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RESEARCH PRODUCT
The equilibrium structure of trans-glyoxal from experimental rotational constants and calculated vibration–rotation interaction constants
René Wugt LarsenFilip PawłowskiFlemming HegelundBengt NelanderPoul JørgensenJürgen Gausssubject
ChemistryGeneral Physics and AstronomyInfrared spectroscopyThermodynamicsSpectral linesymbols.namesakeComputational chemistryKinetic isotope effectsymbolsMoleculeIsotopologueRotational spectroscopyPhysical and Theoretical ChemistryHamiltonian (quantum mechanics)Ground statedescription
A total of six high-resolution FT-IR spectra for trans-glyoxal-d2, trans-glyoxal-d1 and trans-glyoxal-13C2 were recorded with a resolution ranging from 0.003 to 0.004 cm−1. By means of a simultaneous ground state combination difference analysis for each of these isotopologues using the Watson Hamiltonian in A-reduction and Ir-representation the ground state rotational constants are obtained. An empirical equilibrium structure is determined for trans-glyoxal using these experimental ground state rotational constants and vibration–rotation interaction constants calculated at the CCSD(T)/cc-pVTZ level of theory. The least-squares fit yields the following structural parameters for trans-glyoxal: re(C–C) = 1.51453(38) A, re(C–H) = 1.10071(26) A, re(CO) = 1.20450(27) A, αe(CCH) = 115.251(24)°, and αe(HCO) = 123.472(19)° in excellent agreement with theoretical predictions at the CCSD(T)/cc-pVQZ level of theory.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2003-01-01 | Phys. Chem. Chem. Phys. |